D. J. R. Brook, J.-M. Lehn et al.
FULL PAPER
(450.3): calcd. C 69.31, H 5.82, N, 24.87; found C 70.48, H 5.63,
N 29.35.
2 H, H3), 7.80 (dt, J = 7.6 Hz, 2 H, H2Јo), 7.79 (d, J = 3.6 Hz, 2
H, H4), 7.66 (d, J = 3.6 Hz, 2 H, H1), 7.27 (dt, J = 7.6 Hz, 2 H,
H2), 7.07 (dt, J = 7.6 Hz, 2 H, H2Јi), 6.74 (s, 1 H, H5), 6.48 (d, J =
7.3 Hz, 2 H, H1Јo), 5.51 (d, J = 7.3 Hz, 2 H, H1Јi), 2.40 (s, 6 H, R1
= CH3); assignments made on the basis of the COSY and the
2-Phenyl-4,6-bis{[(pyridin-2-yl)methylidene]hydrazino}pyrimidine
1
(10): H NMR (CDCl3, ppm): δ = 9.87 (s, 2 H, R2 = H), 8.69 (d,
J = 3.6 Hz, 2 H, H1), 8.18 (d, J = 3.6 Hz, 2 H, H4), 7.96 (s, 2 H,
R1 = H), 7.68 (dt, J = 7.6 Hz, 2 H, H3), 7.48 (m, 4 H, H1Ј), 7.42
ROESY spectra. ES-MS: m/z (%) = 637 (100) [(84Zn4)(CF3SO3)4]4+
.
(dt, J = 7.6 Hz, 2 H, H2), 7.32–7.34 (m, 6 H), 6.89 (s, 1 H, H5); Complex [94Zn4](CF3SO3)8 (15): 1H NMR (CDCl3, ppm): δ = 7.96
assignments made on the basis of the COSY and the ROESY spec-
tra. 13C NMR (CDCl3, ppm): δ = 12.8, 42.4, 88.9, 124.1, 125.9, J = 7.6 Hz, 2 H, H2Јo), 7.60 (d, J = 3.6 Hz, 2 H, H4), 7.37 (d, J =
127.0, 128.5, 129.0, 135.8, 149.9, 152.5, 155.6 163.8, 170.7. ES-MS:
3.6 Hz, 2 H, H1), 7.06 (dt, J = 7.6 Hz, 2 H, H2), 7.03 (dt, J =
(t, J = 7.6 Hz, 2 H, H3Ј), 7.88 (dt, J = 7.6 Hz, 2 H, H3), 7.72 (dt,
m/z (%) = 395.5 (100) [M + H]+. C22H18N8 (394.5): calcd. C 66.99, 7.6 Hz, 2 H, H2Јi), 6.60 (s, 1 H, H5), 6.56 (d, J = 7.3 Hz, 2 H, H1Јo),
H 4.60, N, 28.41; found C 67.34, H 4.89, N 27.86.
5.18 (d, J = 7.3 Hz, 2 H, H1Јi), 3.80 (s, 6 H, R2 = CH3) 2.57 (s, 6
H, R1 = CH3); assignments made on the basis of the COSY and
the ROESY spectra. ES-MS: m/z (%) = 669.5 (100) [(94Zn4)-
2-Phenylpyrimidine-4,6-dicarbaldehyde Bis[(pyridin-2-yl)hydrazone]
(11): To a solution of 2-phenylpyrimidine-4,6-dicarbaldehyde
(0.201 g, 0.95 mmol) in ethanol (15 mL) was added a solution of
2-hydrazinopyridine (0.206 g) in ethanol (2 mL). A yellow precipi-
tate of 11 formed after about 30 s. The solution was allowed to
stand overnight after which the precipitate was removed by fil-
tration, recrystallized from tetrahydrofuran and dried in air to give
0.370 g of the product (99%).1H NMR ([D6]DMSO, ppm): δ =
(CF3SO3)4]4+
.
Complex [104Zn4](CF3SO3)8 (16): 1H NMR (CDCl3, ppm): δ =
12.09 (s, 6 H, R2 = H) 8.19 (t, J = 7.6 Hz, 2 H, H3Ј), 8.09 (s, 6 H,
R1 = H), 7.89 (s, 1 H, H5), 7.75 (dt, J = 7.6 Hz, 2 H, H3), 7.49 (dt,
J = 7.6 Hz, 2 H, H2Ј), 7.39 (d, J = 3.6 Hz, 2 H, H1), 6.97 (d, J =
3.6 Hz, 2 H, H4), 6.84 (dt, J = 7.6 Hz, 2 H, H2), 5.92 (d, J = 7.3 Hz,
11.62(s, 1 H, NH, exchanges w D2O, R1 = H), 8.42 (m, 2 H, H1Ј), 2 H, H1Јo), 5.82 (d, J = 7.3 Hz, 2 H, H1Јi); assignments made on
8.21 (d, J = 4.11 Hz, 2 H, H1) 8.17 (s, 1 H, H5), 8.11 (s, 2 H, R2 =
H), 7.78 (dd, J = 7.4 Hz, J = 8.2 Hz, 2 H, H3), 7.55 (m, 3 H, H2Ј,
H3Ј) 7.42 (d, J = 8.2 Hz, 2 H, H4), 6.91 (dd, J = 7.4 Hz, J = 4.1 Hz,
2 H, H2). 13C NMR ([D6]DMSO, ppm): δ = 107.5, 107.6, 117.1,
128.4, 129.2, 131.5, 137.6, 137.7, 139.0, 148.5, 156.7, 161.9, 164.2.
the basis of the COSY and the ROESY spectra. ES-MS: m/z (%)
= 610 (100) [(104Zn4)(CF3SO3)4]4+
.
Complex [114Zn4](CF3SO3)8 (17): Ligand 11 (38 mg, 0.1 mmol) and
Zn(OTf)2 (38 mg, 0.11 mmol) gave after recrystallization from ace-
1
tonitrile/diethyl ether, 48 mg (63%) of greenish yellow crystals H
IR (NaCl plate): ν = 1640, 1561, 1439, 751 cm–1. ES-MS: m/z (%)
NMR (CD3CN, ppm): δ = 11.80 (s, 8 H, R2 = H) 8.14 (t, J =
7.6 Hz, 8 H, H3Ј), 8.07 (s, 4 H, H5), 7.88 (s, 8 H, R1 = H), 7.75
(ddd, J = 1.6, 7.4, 8.2, Hz 2 H, H3), 7.45 (t, J = 7.7 Hz, 2 H, H2Ј),
7.39 (dd, J = 0.8 Hz, 5.5, 2 H, H1), 6.98 (d, J = 8.5 Hz, 2 H, H4),
6.83 (td, J = 0.8 Hz, 1.6, 5.5, 2 H, H2), 5.92 (d, J = 7.1 Hz, 2 H,
H1Јo), 5.84 (d, J = 7.1 Hz, 2 H, H1Јi); assignments made on the
basis of the COSY and the ROESY spectra. 13C NMR ([D3]aceto-
nitrile, ppm): δ = 166.1, 157.8, 148.9, 146.1, 142.8, 135.8, 134.0,
131.0, 129.0, 127.1, 123.1, 123.0, 121.0, 120.5, 111.9. ES-MS:
m/z (%) = 545 (100) 395 (45). 114Zn4(CF3SO3)8 (3031.8): calcd. C
˜
= 395 (100) [M – H]+. C22H18N8 (394.5): calcd. C 66.99, H 4.60,
N, 28.41; found C 66.12, H 4.71, N 27.50.
2-Phenylpyrimidine-4,6-dicarbaldehyde Bis[N-methyl-N-(pyridin-2-
yl)hydrazone] (12): Excess sodium hydride (60% dispersion in min-
eral oil) was added to a solution of 11 (419 mg) in tetrahydrofuran.
The yellow solution rapidly turned dark blue-purple. To this solu-
tion was added excess methyl iodide, and the solution was stirred
for 30 minutes during which the color dispersed to give a yellow
solution. The solution was filtered and evaporated, and the residue
washed with hexane to give 435 mg (97%) of 12. 1H NMR (CDCl3, 38.03, H 2.39, N, 14.78; found C 37.13, H 2.37, N 14.51.
ppm): δ = 3.74 (s, 6 H, R1 = CH3) 6.89 (ddd, J = 1.0, J = 5.0, J =
Complex [124Zn4](CF3SO3)8 (18): Ligand 12 (42 mg, 0.1 mmol) and
Zn(OTf)2 (38 mg, 0.1 mmol) gave after recrystallization from aceto-
7.0 Hz, 2 H, H2), 7.49 (m, 3 H, phenyl) 7.65 (ddd, J = 1.8, J = 7.0,
J = 8.6 Hz, 2 H, H3), 7.72 (s, 2 H, R2) 7.85(d, J = 8.6 Hz, 2 H,
H4), 8.28 (ddd, J = 1.0, J = 1.8, J = 1.8 Hz, 2 H, H1), 8.33 (s, 1 H,
H5), 8.5 (m, phenyl). 13C NMR (CDCl3, ppm): δ = 30.03, 107.75,
110.44, 128.26, 128.61, 130.57, 132.98, 137.62, 138.01, 147.23,
nitrile/diethyl ether, 55 mg (68%) of orange crystals with 1H NMR
(CD3CN, ppm): δ = 8.16 (t, J = 7.6 Hz, 4 H, H3Ј), 8.14 (s, 8 H,
H5), 7.86 (m, 16 H, R1 = H, H3), 7.53 (t, J = 7.4 Hz, 4 H, H2Јo),
7.34 (m, 12 H, H1,H2Јi), 7.29 (d, J = 8.5 Hz, 8 H, H4), 6.93 (dd, J
= 6.7 Hz, 5.4, 8 H, H2), 5.89 (d, J = 7.4 Hz, 4 H, H1Јo), 5.81 (d, J
= 7.7 Hz, 4 H, H1Јi), 3.51 (s, 24 H, R2 = CH3). 13C NMR (ppm):
δ = 165.8, 157.9, 149.5, 146.8, 143.2, 135.1, 133.8, 130.2, 129.7,
129.0, 127.7, 123.8, 122.0, 121.1, 111.7, 34.0; assignments made on
the basis of the COSY and the ROESY spectra. ES-MS: m/z (%)
mass envelope at 637 (100) [(124Zn4)(CF3SO3)4]4+: calcd. C 39.73,
H 2.82, N 14.26; found C 37.83 H 2.54 N 13.46
157.21, 162.19. IR (NaCl plate): ν = 1624 cm–1 (C=N). ES-MS:
˜
m/z (%) = 423 (50) [M + H]+, 421 (100), 242 (100). C24H22N8
(422.5): calcd. C 68.23, H 5.25, N, 26.52; found C 67.04, H 5.35,
N 25.57.
General Procedure for the Formation of the [2×2]Zn2+ Grid-Type
4
Complexes 13–18: An equimolar mixture of Zn(CF3SO3)2 and of
the ligands 7–12 in acetonitrile was stirred at room temperature for
5 h. The complexes were obtained by crystallization with diisopro-
pyl ether or diethyl ether.
Complex [112–4Zn4] (19) Method 1: 2-Phenylpyrimidine-4,6-di-
carbaldehyde bis[(pyridin-2-yl)hydrazone], (0.11 g, 0.28 mmol) was
suspended in EtOH (20 mL), and a solution of anhydrous ZnCl2
(0.04 g ) in EtOH (1 mL) was added. After stirring 5 min, the dark
brown solution was made basic by the addition of 2 equiv. NaOH
whereupon the mixture turned blue-purple. Evaporation left a dark
Complex [74Zn4](CF3SO3)8 (13): 1H NMR (CDCl3, ppm): δ = 8.01
(t, J = 7.6, 2 H, H3Ј), 7.98 (s, 2 H, R1 = H), 7.87 (dt, J = 7.6 Hz,
2 H, H3), 7.78 (dt, J = 7.6 Hz, 2 H, H2Јo), 7.65 (d, J = 3.6 Hz, 2
H, H1), 7.60 (d, J = 3.6 Hz, 2 H, H4), 7.25 (dt, J = 7.6 Hz, 2 H,
H2), 7.18 (dt, J = 7.6 Hz, 2 H, H2Јi), 6.84 (s, 1 H, H5), 6.49 (d, J = purple-bronze solid that was purified by dissolution in THF, fil-
7.3 Hz, 2 H, H1Јo), 5.44 (d, J = 7.3 Hz, 2 H, H1Јi), 3.67 (s, 6 H, R2
tration and evaporation of the filtrate. The residue was recrys-
tallized from water/EtOH to give small, golden, pyramidal crystals
(85 mg, 66%)
= CH3); assignments made on the basis of the COSY and the
ROESY spectra. ES-MS: m/z (%) = 637 (100) [(74Zn4)(CF3SO3)4]4+
.
Complex [84Zn4](CF3SO3)8 (14): 1H NMR (CDCl3, ppm): δ = 10.97
Method 2: Complex 17 (20 mg) was dissolved in acetonitrile (2 mL)
and excess triethylamine (10 µL) was added. The solution immedi-
(s, 2 H, R2 = H), 8.05 (t, J = 7.6 Hz, 2 H, H3Ј), 7.76 (dt, J = 7.6 Hz,
790
www.eurjic.org
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2006, 784–792